The microstructural analysis of the dehydrogenation products of the Ca(BH₄)₂-MgH₂ composite was performed using transmission electron microscopy. It was found that nanocrystalline CaB₆ crystallites formed as a dehydrogenation product throughout the areas where the signals of Ca and Mg were simultaneously detected, in addition to relatively coarse Mg crystallites. The uniform distribution of the nanocrystalline CaB₆ crystallites appears to play a key role in the rehydrogenation of the dehydrogenation products, which implies that microstructure is a crucial factor determining the reversibility of reactive hydride composites.